Bis [9-(3-aminoalkyl) fluoren-9-yl] alkanes



United States Patent 3,299,140 BIS[9-(3-AMlNOALKYL)FLUOREN-9-YL]ALKANESHenry E. Fritz, South Charleston, and David W. Peck,

Charleston, W. Va., assignors to Union Carbide Corporation, acorporation of New York No Drawing. Original application Sept. 10, 1062,Ser. No. 222,694, now Patent No. 3,205,257, dated Sept. 7, 1965. Dividedand this application Mar. 8, 1965, Ser.

2 Claims. or. 260-5703) This invention relates to novel fluorenederivatives. More particularly, this invention relates tobis[9-(substituted alkyl)fluoren-9-yl] alkanes of the formula:

wherein n is an integer having a value of from to and preferably from 2to 6; Z is a cyano radical, a -COOR radical, or a CH NHR radical; R is ahydrogen atom or a methyl radical, i.e., a radical of the formula C Hwherein x is an integer having a value of from 0 to 1; R is a hydrogenatom, an alkali metal atom, or an alkyl radical having from 1 to about10 carbon atoms; and R is a hydrogen atom or an alkanoyl radical havingfrom 1 to about carbon atoms in the alkyl radical thereof. Thus, thecompounds of this invention are novel bis[9-(2-cyanoalkyl)fluoren-9yIJalkanes; bis [9-(2-carboxyalkyl)fiuoren-9-yl]alkanes and their alkalimetal salts or alkyl esters;bis[9-(N-alkanoyl-3-aminoalkyl)fluoren-9-yl] alkanes; andbis[9-(3-aminoalkyl)fluoren-9-yl]alkanes. This application is a divisionof application Serial No. 222,694, filed September 10, 1962, now U.S.Patent No. 3,205,257.

The novel carboxyl and amino compounds of this invention are useful inthemselves as monomers for the formation of new polymers, such aspolyesters, polyamides, and the like; while the cyano compounds areuseful as intermediates for the production of polymerizable monomers.For example, the cyano derivatives of this invention can be hydrolyzedto form dicarboxylic acids which are useful in the production-ofpolyesters or polyamides. The cyano derivatives can also be hydrogenatedin the presence of an alkali metal alkanoate to produce N- alkanoylaminoderivatives which can be hydrolyzed to form an amine derivative usefulin the production of polyamides, polyureas, and the like.

The novel bis [9-(substituted alkyl)fluoren-9-yl]alkanes of thisinvention are all readily produced from the bis(9- fiuorenyl)alkanes ofthe formula:

wherein n is as previously defined. The bis(9-fiuorenyl) alkanes areproduced by reacting a fluorene with a diol in the presence of an alkalimetal hydroxide as a catalyst.

The fluorene compounds may be substituted on the aromatic rings withalkyl, aryl, alkaryl, aralkyl, alkoxy, aryloxy, alkaryloxy, and aralkoxyradicals having up to carbon atoms. As examples of suitable fluorenecompounds, one can mention fluorene, l-methylfluorene, 2-methylfluorene, 3-methylfluorene, 4-methylfluorene, 5- methylfiuorene,6-methylfiuorene, 7-methylfluorene, 8- methylfiuorene, 2-hexylfluorene,Z-phenylfluorene, 2-(1- naphthyl)fluorene, 2-(2-methylphenyl)fluorene,2-benzylfluorene, 2-methoxyfluorene, 2-phenoxyfluorene, 2-(2-methylphenoxy)fluorene, 2-benzyloxyfluorene, and the like.

The diols employed to produce the bis(9-fluorenyl)- alkanes arerepresented by the formula uoc n on wherein n is as defined above. Asexamples of suitable diols one can mention ethylene glycol, propyleneglycol, tetramethylene diol, decamethylene diol, pentamethylene diol,hexamethylene, diol, and the like. In producing thebis(9-fluorenyl)alkanes the concentration of diol in the charge can varyfrom about 0.1 mole or less to about 10 moles or more, per mole offluorene compound charged, with from about 0.5 to about 2.0 mole of diolper mole of fluorene compound being preferred.

As stated above, an alkali metal hydroxide, such as lithium hydroxide,sodium hydroxide, potassium hydroxide, and the like, is employed as acatalyst in producing the bis(9-fluorenyl)alkanes, with potassiumhydroxide being preferred. The amount of alkali metal hydroxide used canvary from about 0.1 mole or less to about 1.0 mole or more per mole offluorene compound charged, with from .about 0.2 to about 0.5 mole ofalkali metal hydroxide per mole of fluorene compound being preferred.The reaction of diol with fluorene is conducted at a temperature of fromabout C. or lower to about 275 C. or higher, with temperatures of fromabout 220 C. to about 250 C. being preferred.

The bis(9-fluorenyl)alkane is readily recovered from the reactionmixture by slurrying the reaction mixture with water to dissolveunreacted diol and the alkali metal hydroxide and then filtering theinsoluble bis(9-fluorenyl)alkanes from the aqueous slurry. If desired,the bis(9-fiuorenyl)alkane can be further purified by washing with wateror methanol, or by recrystallization from an organic solvent, forexample, 1,4-dioxane.

Reaction of the bis(9-fluorenyl)alkane with a cyanoalkene such asacrylonitrile or methacrylonitrile produces thebis[9-(2-cyanoa1ky1)fluoren-9-yl]alkanes having the formula:

onus. CHZCHRCN wherein n and R are previously defined. As examples ofthese compounds one can mention 1,2-bis[9-(2Fcyanoethyl)fluoren-9-yl1ethane, 1,4 bis[9-2-cyanoethyl)fluoren-9-yl1b-utane, 1,10 bis[9-(2-cyanoethyl)fluoren-9- yl] decane,1,2-bis [9- 2-cyanopropyl) fluoren-9-yl] ethane, 11i{10bis[9-(2eyanopropyl)fluoren-9-yl]decane, and the As indicated, thebis[9 (2 cyanoalkyl)fluoren-9-yl] alkanes are produced by thecyanoalkylation of a bis(9- fluorenyl)alkane with a cyanoalkene such asacrylonitrile or methacrylonitrile. The cyanoalkylation can be carriedout at from about 10 C. to about 50 C., preferably from about 20 C. toabout 35 C., in the presence of a solvent for the bis(9-fluorenyl)alkane, for example benzene, dioxane, pyridine, acetonitrile, tert-butylalcohol, etc. The mole ratio of cyanoalkene to bis'(9- fluorenyl) alkanecan vary from about 0.5: l or less to about 5:1 or more, with ratios offrom about 2:1 to about 3:1 preferred. The cyanoalkylation is assistedby a basic catalyst, such as the oxides, hydroxides, alkoxides,hydrides, cyanides, or amides of sodium or potassium. Quaternaryammonium hydroxides such as benzyltrimethylammonium hydroxide areparticularly preferred as catalysts. In general, the basic catalysts areemployed in the cyanoalkylation reaction in an amount varying from about0.5 to about 10 weight percent, based upon the NC CHRCH;

cyanoalkene, with from about 1 to about weight percent preferred.Although the reactants can be charged in any order, it is preferred togradually add the cyanoalkene to a stirred mixture catalyst,bis(9-fluorenyl)alkane and solvent.

The bis[9-(2-cyanoalkyl)fluoren-9-yl1alkanes are solids which can berecovered from the reaction mixture by filtration. Additionalbis[9-(2-cyanoalkyl)fiuoren-9-yl] alkane can be recovered from thefiltrate by admixing the filtrate with water, whereupon thebis[9-(2-cyanoalkyl) fluoren-9-yl] alkane dissolved in the filtrateprecipitates out and can be recovered by filtration. Thebis[9-(2-cyanoalkyl) )fiuoren-9-yl]alkane can then be purified byconventional procedures.

The bis[9-(2-carboxyalkyl)fluoren-9-yl]alkanes and the alkali metalsalts and alkyl esters thereof of this invention have the formula:

IUOOCCHRCH CD11 OHZCHROOORI wherein n, R and R are as defined above.

As examples of the novel dicarboxylic acids one can mention 1,2bis[9-(2-carboxyethyl)fluoren-9-yl]ethane,1,4-bis[9-(2-carboxyethyl)fluoren-9-yl]butane, 1,10-bis [9-(2-carboxyethyl) fiuoren 9 yl]decane,l,2-bis[9-(2-carboxypropyl)fluoren-9-yl]ethane, 1,10bis[9-(2-carboxypropyl)fluoren-9-yl1decane, and the like. Thesedicarboxylic acid compounds are readily produced by the hydrolysis ofthe corresponding bis [9-(2-cyanoalkyl) fiuoren-9-yl1alkane compound orby the reaction of an alkali meta-l acrylate or alkali metalmethacrylate with a bis(9-fluorenyl)alkane followed by acidification ofthe resulting dialkali metal salt.

The hydrolysis of the bis[9-(2-cyanoalkyl)fluoren-9- yl]alkane to formthe bis[9-(Z-carboxyalkyl)fluoren-9- yl]alkane can be conducted bymethods known to those skilled in the art of the hydrolysis of thenitrile group. It is preferred, however, to reflux thebis[9-(2-cyanoalkyl)fluoren9-yl] alkane in admixture with water, aceticacid, and hydrobromic acid, there being at least four moles of water andat least two moles of hydrobromic acid per mole ofbis[9-(2-cyanoalkyl)fluoren-9-yl]alkane in the charge.

As indicated above, the bis[9-(2-carboxyalkyl)fiuoren- 9-yl]alkane alsocan be produced by reacting an alkali metal acrylate or alkali metalmethacrylate with a bis(9- fiuorenyl)alkane in the presence of an alkalimetal hydroxide as a catalyst. The mole ratio of alkali metal acrylateor alkali metal methacrylate to bis(9-fiuorenyl) alkane in the chargecan 'vary from about 1:1 to about 5:1, with a mole ratio of from about2:1 to about 3:1 preferred. The alkali metal hydroxide is employed in anamount varying from about 0.1 to about 5 weight percent, based uponalkali metal acrylate or alkali metal methacrylate, with from about 0.5to about 3 weight percent preferred. The reaction is conducted at atemperature of about 150 C. to about 350 C., with a temperature of fromabout 190 C. to about 290 C. preferred. The immediate products of thisprocess are the dialkali metal salts of thebis[9-(2-carboxyalkyl)fiuoren-9-yl] alkanes such as the lithium, sodium,potassium, rubidium or cesium salts. These dialkali metal salts arereadily acidified by methods known to those skilled in the art toproduce the corresponding bis[9 (2-carboxyalkyl)fiuoren- 9-yl]-alkane.

The bis[9-(2-carboxyalkyl)fiuoren 9 yl] alkanes are water-insolublesolids. Thus, they can be isolated from the reaction mixture from eitherof the foregoing processes by the addition of water and filtration ofthe aqueous mixture.

The bis[9-(2-carboxyalkyl)fiuoren 9 yl]alkanes are readily converted totheir alkyl esters, of the formula:

IUOOCGHRCH nHZn CHZCHRCOOR R ONHCH OHRCH CuHZn CHzCHRCHzNHCR wherein nand R are as previously defined and R is an alkyl radical of from 1 to 5carbon atoms. As examples of these compounds one can mention1,2-bis[9-(N-acetyl- 3-aminopropyl)fluoren-9-yl]et hane,l,4-bis[9-(N-acetyl-3- aminopropyl)fluoren-9-yl]butane,1,10-bis[9-(N-acetyl-3- aminopropyl)fluoren-9-yl]ethane,l,2-bis[9-(N-valeryl-3 aminopropyl)fluoren-9-yl]ethane,1,2-bis[9-(N-acetyl-3- amino-Z-methylpropyl)fluoren-9-yl] ethane, andthe like.

The bis[9 (N alkanoyl-3-aminoalkyl)fluoren-9-yl] alkanes of thisinvention are produced, for example, by hydrogenation of a mixture of abis[9-(2-cyanoalkyl) fluoren-9-yl]alkane, an alkanoic acid anhydride andan alkali metal alkanoate in contact with hydrogenation catalys-t.

The alkanoic acid anhydridcs suitable for use in producing thebis[9-(N-alkanoy1-3-aminoalkyl)fluoren-9-yl] alkanes of this inventionare the anhydrides of lower alkanoic acids such as acetic acid,propionic acid, butyric acid, pentanoic acid, and the like. In thisreaction, the mole ratio of acid anhydride to bis[9-(2-cyanoalkyl)fiuoren-9-yl1alkane can vary from about 0.5 :1 or less to about 4:1 orhigher, with mole ratios of from about 1:1 to about 2:1 preferred.

The alkali 'metal alkanoate employed is preferably the alkali metal saltof the alkanoic acid whose anhydride is employed during thehydrogenation reaction. The alkali metal salts can be the lithium,sodium, potassium, rubidium, or cesium salts of the alkanoic acid. Asexamples of suitable alkali metal alkanoates one can mention lithiumacetate, sodium acetate, potassium acetate, rubidium acetate, cesiumacetate, sodium propionate, sodium butyrate, sodium valerate, and thelike. In general, the alkali metal alkanoates are present in thereaction mixture in an amount varying from 5 to 100 weight percent basedon the bis[9-(Z-cyanoalkyl)fluoren-9-yl] alkane, with from 10 to 30weight percent preferred.

The hydrogenation catalyst can be any of the Raney metal catalysts knownto the art, with Raney nickel being preferred. The catalyst is employedin amounts varying from 2 to 40 weight percent, based on the bis[9-(2-cyanoalkyl)fiuoren-9-yl]alkane, with amounts of from 10 to 30 percentbeing preferred. The hydrogenation is carried out at hydrogen pressuresvarying from 40 to 100 p.s.i.g., or more, with pressures of from about50 to about 75 p.s.i.g. being preferred, and at reaction temperatures offrom about 25 C to about 100 C., with temperatures of from about 30 C.to about C. being preferred.

The bis[9-(3-aminoalkyl)fl'uoren-9-yl] alkanes of this invention arerepresented by the formula:

wherein n and R as previously defined. As examples of these noveldiami'nes one can mention 1,2-bis[9-(3-arninopropylyfluoren 9-yl]ethane,1,4-bis[9-(3-aminopropyl) fluoren-9-yl1butane,1,10-bis[9-(3-aminopropyl)fluoren-9- yl] decane, 1,2-bis 9-(3-amino-2-methylpropyl)fluoren-9- yl]ethane, and the like.

The bis[9-(3-aminoalkyl)fluoren-9-yl] alkanes of this invention arereadily produced by hydrolysis of the bis[9-(N-alkanoyl-3-aminoalkyl)fluoren-9-yl]alkanes of the invention. Thehydrolysis can be accomplished by methods known to those skilled in theart, such as by heating in contact with a mixture of aqueous sodiumhydroxide and methanol at a temperature of from about 150 C. to 250 C.

The bis[9-(3-aminoalkyl)fluoren-9-yl]alkanes can also be produced byreduction of the bis[9-(2-cyanoalkyl) fluoren-9-yl1alkanes of thisinvention, such as by the lithium aluminum hydride reduction of thebis[9-(2-cyanoalkyl fluoren-9-yl] alkanes.

The following examples are illustrative:

EXAMPLE I 1,2-bis(9-flu0renyl) ethane A three-liter rocker autoclave wascharged with 332 grams of fluorene, 500 grams of ethylene glycol, and 85grams of potassium hydoxide. The autoclave was sealed, pressured to 25p.s.i.g. with air and heated at 220 C. for 20 hours while agitating byrocking. The autoclave was cooled, opened and the contents were removedand slurried in 1 liter of water. After filtration from the aqueousslurry, washing with water and then with methanol and drying, the1,2-bis(9-fluorenyl)ethane produced weighed 157 grams and melted at 228-229.5 C.

EXAMPLE II 1,6-bis(9-flu0renyl) hexane Employing apparatus andprocedures similar to those disclosed in Example I, 166 grams offluorene, 70 grams of 1,6-hexanediol and 42.5 grams of potassiumhydroxide were reacted at 210220 C. for 4 hours to produce 143 grams of1,6-bis(9-fluorenyl)hexane. After recrystallizing from a mixture ofisopropanol and dioxane the 1,6- bis(9-fluorenyl)hexane melted at109109.5 C.

EXAMPLE III 1,2-bis [9- (Z-cyanoethyl)fluoren-9-yl] ethane To a chargecontaining 36 grams of 1,2-bis(9-fluorenyl) ethane, 750 cc. of dioxaneand 10 cc. of a 32 percent solution of benzyltrimethylammonium hydroxidein methanol as a catalyst, there were slowly added grams ofacrylonitrile with stirring. The temperature of the reaction mixturerose from 27 C. to 37 C. After cooling to 29 C. and stirring for another2 hours, an additional 10 cc. of the benzyltrimethylammoniumhydroxidemethanol solution and 20 grams of acrylonitrile were added. Thereaction mixture was filtered and the solid 1,2 bis[9-(2cyanoethyl)fluoren 9 ylJethane was recovered, which, afterrecrystallization from dioxane, weighed 26 grams and melted at 275-277C. Microanalysis.Calculated for C H N C, 89,94%; H, 6.03%; N, 6.03%.Found: C, 89.95%; H, 6.10%; N, 6.20%. The structure of thel,2-bis[9-(2-cyanoethyl) fluoren-9-yl1ethane was further confirmed byinfrared spectroscopy.

In a similar manner, 1,2-bis[9-(2-cyanopr0pyl)fluoren- 9-yl]ethane isproduced by substituting methacrylonitrile for acrylonitrile.

EXAMPLE IV 1,5-bis [9- (Z-cyanoethyl) flu0ren-9-yl] pentane Employingapparatus and procedures similar to those described in Example III, 30grams of 1,5-bis(9-fluorenyl) pentane (produced in a manner similar tothat described in Example I by reacting fluorene with 1,5-pentane diolin the presence of potassium hydroxide) were reacted with 16 grams ofacrylonitrile to produce 26 grams of 1,5-bis[9-(Z-cyanoethyl)fluoren-9-yl1pentane which, after recrystallizationfrom methanol, melted at l21 C. Microanalysis.Calculated for C H N C,87.61%; H, 6.76%; N, 5.53%. Found: C, 88.01%; H, 6.69%; N, 5.65%.

EXAMPLE VI Employing apparatus and procedures similar to those describedin Example III, 34 grams of 1,6-bis (9-fluorenyl) hexane were reactedwith 16 grams of acrylonitrile to produce 31 grams of1,6-bis[9-(Z-cyanoethyl)fiuoren-9-yl] hexane which, afterrecrystallization from methanol, melted at 125.5-126.5 C.

Microanalysis. Ca1culated for C H N C, 87.66%; H, 6.23%; N, 5.38%.Found: C, 87.38%; H, 6.90%; N,

EXAMPLE VII 1,2-bis[9- (Z-carboxyethyl)fluoren-Q-yl] ethane A mixture of300 grams of 1,2-bis[9-(2-cyanoethyl) fluoren-9-yl1ethane, 750 grams ofacetic acid and 750 grams of aqueous 48 percent hydrobromic acid ascatalyst was refluxed vigorously for 4 days. After filtration from thereaction mixture, washing with water and recrystallization from dioxane,there were obtained 277 grams of1,2-bis[9-(2-carboxyethyl)fluoren-9-yl]ethane which melted at 285-287 CMicr0analysis.Calculated for Found: C, 81.02%; H, 6.09%.

The structure of the 1,2bis[9-(2-carboxyethyl)fluoren-9- yl] ethane wasfurther confirmed by infrared spectroscopy.

In a similar manner, 1,2-bis[9-(2-carboxypropyl)fluoren-9-yl1ethane isproduced by substituting 1,2-bis[9-(2- cyanopropyl)fluoren-9-yl]ethanefor 1,2-bis [9-(2-cy anoethyl)fluoren-9-yl1ethane.

EXAMPLE VIII 1 ,4-bis[9- (Z-earboxyethyl) fluoren-Q-yl] butane Employingapparatus and procedures similar to those described in Example VII, 10grams of 1,4-bis[9-(2-cyanoethy1)fluoren-9-yl]butane, 200 milliliters ofacetic acid and 200 milliliters of aqueous 48 percent hydrobromic acidwere refluxed for 16 hours to produce 8 grams of 1,4 bis[9(2-carboxyethyl)fluoren 9 yl]butane which, ggter recrystallization fromisopropanol, melted at 261- 7 Microanalysis.-Calculated for C H O C,81.48%; H,

6.45%. Found: C, 81.49%; H, 6.51%.

EXAMPLE IX 1 ,5-bis [9- (Z-carboxyethyl) fluren-9-yl] pen lane Employingapparatus and procedures similar to those described in Example VII,grams of 1,5-bis[9-(2-cyanoethyl)fluoren-9-yl1rpentane, 200 millilitersof acetic acid and 200 milliliters of aqueous 48 percent hydrobromicacid were refluxed for 16 hours to produce 10 grams of 1,5bis[9-(2-carboxyethyl)fluoren 9 yl]pentane which, afterrecrystallization from a cyclohexane-benzene-isopropanol mixture, meltedat 180-181 C.

Microanalysis.Calculated for C3'1H36O4: C, 81.58%; H,

6.66%. Found: C, 81.34%; H, 6.69%.

EXAMPLE X 1,6-bis [9- (Z-carboxyethyl)flu0ren-9-yl] hexane Employingapparatus and procedures similar to those described in Example VII, 10grams of 1,6-bis[9-(2-cyanoethyl)fiuoren-9-yl]hexane, 200 milliliters ofacetic acid, and 200 milliliters of aqueous 48 percent hydrobromic acidwere refluxed for 16 hours to produce 10 grams of1,6-bis[9-(2-carboxyethyl)fluoren-9-yl1hexane which, afterrecrystallization from isopropanol, melted at 218 219 C.

Microanalysis.Calculated for C H O C, 81.69%; H,

6.86. Found: C, 81.75%; H, 7.11%.

EXAMPLE XI 1,2-bis [9- (Z-em-boxyethyl)flu0ren-9-yl] ethane1,2-bis[9-(2-carboxyethyl)fluoren 9 yl]eth ane is pro duced by reacting1,2-bis(9-fluorenyl)ethane with potassium acrylate in the presence ofpotassium hydroxide at about 300 C. to produce the dipotassium salt of1,2- bis[9-(Z-carboxyethyl)fiuoren-9-yl]ethane and acidifying thereaction mixture with aqueous hydrochloric acid to liberate the freeacid.

In a similar manner, 1,2-bis[9-(2-carboxypropyl)fiuoren- 9- yl]ethane isproduced by substituting potassium methacrylate for potassium acrylate.

EXAMPLE XII 1 ,6-bis [9- (N -acetyl-3 -amin0pr0pyl flu0ren-9-yl hexane Ahydrogenating vessel was charged with 10 grams of1,6-bis[9-(2-cyan0ethyl)fluoren-9-yl]hexane, 100 grams of aceticanhydride, 2 grams of sodium acetate and about 3 grams of neutral Raneynickel catalyst. The hydrogenator was sealed, pressured to 59.5 p.s.i.g.with hydrogen and heated at 80 C. for 6 hours, over which time thehydrogen pressure decreased to 52 p.s.i.g. The hydrogenator was cooled,opened, and the contents were filtered to remove the Raney nickel. Thefiltrate was added to 500 milliliters of water, whereupon the 1,6- bis[9(N-acetyl-3-aminopro1pyl)fiuoren-9-yl]hexane produced precipitated.After filtration and recrystallization from hexane-isopropanol mixture,it Weighed 10 grams and melted at 176179 C. After two additionalrecrystallizations from a hexane-isopropanol mixture the 1,6- bis[9(N-acetyl 3 aminopropyl)fiuoren 9 yllhexane melted at 177-180 C.

Microanalysis.Calculated for C H O C, 82.4%; H,

7.9%; N, 4.6%. Found: C, 82.4%; H, 8.0%; N. 4.2%.

8 EXAMPLE x111 1 ,Z-bis [9- (N -ace tyl-3 -amin0 propyl fluOren-9-ylethane Employing apparatus and procedures similar to those described inExample XII, 10 grams of 1,2-bis[9-(2-cyanoethyl)fluoren-9-yl]ethane,grams of acetic anhydride, 2 grams of sodium acetate and about 3 gramsof Raney nickel catalyst were hydrogenated at 35-45 C. for 5 hours toproduce 9 grams of 1,2-bis[9-(N-acetyl3-aminopropyl)fluoren-9-yl1ethane,which, after recrystallization from dioxane, melted at 267.5269.5 C.

Micr0analysis.Calculated for C H N O C, 82.0%; H, 7.2%; N, 5.0%. Found:C, 81.8%; H, 7.1%; N, 4.7%.

In a similar manner 1,2-bis[9-(N-acetyl-3-amino-2-methylpropyDfiuoren-9-yl] ethane is produced by substituting1,2-bis[9-(2-cyanopnopyl)fiuoren-9-yl]ethane for 1,2-bis[9-(2-cyanoethyl)fluoren-9-yl]ethane, and 1,2-bis[9-(N-valeryl-3-aminopropyl)fluoren-9-yl]ethane is produced by substitutingvaleric anhydride for acetic anhydride and sodium valerate for sodiumacetate.

Microanalysis.Calculated for C H N C, 86.4%; H, 7.7%; N. 5.9%. Found C,86.0%; H, 7.5%; N. 6.0%.

The structure of the 1,2-bis[9-(3-aminopropyl)fiuoren-9- yIJethane wasfurther confirmed by infrared spectroscopy.

In a similar manner,1,2-bis[9-(3-amino-2-rnethylpropyl)fluoren-9-yl]eth-ane is produced bysubstituting 1,2- bis[9 (N acetyl 3 amino 2 methylpropyl)fluoren-9-yl]ethane for 1,2-bis[9-(N-acetyl-3-aminopropyl)fluoren-9-yl] ethane.

What is claimed is:

1. A bis[9-(3-aminoalkyl)fluoren-9-yl]alkane of the formula:

wherein n is an integer having a value of from 2 to 10 and x is aninteger having a value of from 0 to 1.

2. 1,2-bis[9-(3-aminopropyl)fluoren-9-yl1ethane.

No references cited.

CHARLES B. PARKER, Primary Examiner.

R. V. HINES, N. T, ROUSOF, Assistant Examiners.

1. A BIS(9-(3-AMINOALKYL)FLUOREN-9-YL)ALKANE OF THE FORMULA:9-((9-(H2N-CH2-CH(-CXH2X+1)-CH2-)-FLUOREN-9-YL)-CNH2N-),9-(H2N-CH2-CH(-CXH2X+1)-CH2-)-FLUORENE WHEREIN N IS AN INTEGER HAVING AVALUE OF FROM 2 TO 10 AND X IS AN INTEGER HAVING A VALUE OF FROM 0 TO 1.